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DE4042009A1 - METHOD AND DEVICE FOR THE BIOLOGICAL PROCESSING OF WASTE RUBBER - Google Patents

METHOD AND DEVICE FOR THE BIOLOGICAL PROCESSING OF WASTE RUBBER

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Publication number
DE4042009A1
DE4042009A1 DE19904042009 DE4042009A DE4042009A1 DE 4042009 A1 DE4042009 A1 DE 4042009A1 DE 19904042009 DE19904042009 DE 19904042009 DE 4042009 A DE4042009 A DE 4042009A DE 4042009 A1 DE4042009 A1 DE 4042009A1
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DE
Germany
Prior art keywords
rubber
sulfur
bacterial suspension
bioreactor
waste
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
DE19904042009
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German (de)
Other versions
DE4042009C2 (en
Inventor
Willi Prof Dr Sc Techn Neumann
Gunhild Prof Dr Sc Nat Straube
Helmut Dr Rer Nat Rueckauf
Ralf Dipl Ing Forkmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HOELZEMANN METALLVERARBEITUNG GMBH, 57567 DAADEN,
Original Assignee
TECH HOCHSCHULE C SCHORLEMMER
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Publication date
Application filed by TECH HOCHSCHULE C SCHORLEMMER filed Critical TECH HOCHSCHULE C SCHORLEMMER
Priority to DE19904042009 priority Critical patent/DE4042009C2/en
Priority to DE59107689T priority patent/DE59107689D1/en
Priority to DK91121471T priority patent/DK0493732T3/en
Priority to AT91121471T priority patent/ATE136942T1/en
Priority to ES91121471T priority patent/ES2086468T3/en
Priority to EP19910121471 priority patent/EP0493732B1/en
Priority to CA 2058160 priority patent/CA2058160C/en
Priority to US07/811,629 priority patent/US5275948A/en
Priority to JP34059291A priority patent/JP2546942B2/en
Publication of DE4042009A1 publication Critical patent/DE4042009A1/en
Priority to GR960401305T priority patent/GR3019940T3/en
Application granted granted Critical
Publication of DE4042009C2 publication Critical patent/DE4042009C2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M27/00—Means for mixing, agitating or circulating fluids in the vessel
    • C12M27/02—Stirrer or mobile mixing elements
    • C12M27/06—Stirrer or mobile mixing elements with horizontal or inclined stirrer shaft or axis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/105—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with enzymes
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20—Bacteria; Culture media therefor
    • C12N1/205—Bacterial isolates
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P1/00—Preparation of compounds or compositions, not provided for in groups C12P3/00 - C12P39/00, by using microorganisms or enzymes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2319/00—Characterised by the use of rubbers not provided for in groups C08J2307/00 - C08J2317/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12R—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES C12C - C12Q, RELATING TO MICROORGANISMS
    • C12R2001/00—Microorganisms ; Processes using microorganisms
    • C12R2001/01—Bacteria or Actinomycetales ; using bacteria or Actinomycetales
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S241/00—Solid material comminution or disintegration
    • Y10S241/31—Rubber preparation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/911—Recycling consumer used articles or products
    • Y10S264/912—From toroidal shapes, e.g. resilient tires
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S425/00—Plastic article or earthenware shaping or treating: apparatus
    • Y10S425/046—Scrap

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Biotechnology (AREA)
  • Genetics & Genomics (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Microbiology (AREA)
  • Sustainable Development (AREA)
  • Biomedical Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Virology (AREA)
  • Tropical Medicine & Parasitology (AREA)
  • Mycology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Processing Of Solid Wastes (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)

Abstract

There is a processing of old rubber in which regenerated rubber is produced from comminuted old rubber with devulcanisation. It is desirable in this connection for the processing to be biotechnological. This is achieved by keeping the comminuted old rubber in a bacterial suspension of chemolithotrophic microorganisms with introduction of air until sulphur has separated as elemental sulphur and/or sulphuric acid from the remaining replasticised regenerated rubber. This biotechnological processing produces in a simplified manner regenerated rubber and sulphur, both of which can be reused.

Description

Jährlich fallen weltweit mehrere Millionen Tonnen Alt­ gummi, insbesondere alte Autoreifen an, die bisher nur unzureichend als Sekundärrohstoff genutzt bzw. ohne jegliche Verwertung auf Deponien gelagert wurden. Auf­ grund des geringen Anteils des durch verschiedene Aufarbeitungsvarianten, z. B. Runderneuerung von Reifen, in den Stoffkreislauf zurückgeführten Gummis kam es zu einer mengenmäßigen Anhäufung von Altreifen auf Depo­ nien, die einer Aufarbeitung bedürfen.Every year, several million tons of waste fall worldwide rubber, especially old car tires, which so far only insufficiently used as a secondary raw material or without any recycling has been stored in landfills. On due to the small proportion of the different Refurbishment variants, e.g. B. retreading tires, rubber was returned to the material cycle a quantitative accumulation of used tires on Depo nien that need to be processed.

Bisher wurde davon ausgegangen, daß es sich bei Altreifen um natür­ lich unzersetzliche Abfallstoffe handelt (DE 26 38 387).So far assumed that old tires are natural Lich irreplaceable waste materials (DE 26 38 387).

Die bisherige Aufarbeitung der Altreifen erfolgt auf drei verschiedenen Verfahrenswegen:The old tires have been refurbished to date three different procedures:

Als erstes werden die Altreifen nach einer Granulierung bis zu Korngrößen von etwa 25 mm als Zusatz zur Herstel­ lung von bituminösen Straßendeckschichten oder Sport­ platzbefestigungen verwendet. Dazu wird das Gummigranu­ lat in den im Straßenbau üblichen Mischern mit Zement, Kiessand oder Sand, Wasser und Haftverbesserern gemischt und mit den üblichen Straßenbaumaschinen als hochela­ stische Zwischenschicht, beispielsweise bei der Auto­ bahnrekonstruktion oder beim Straßengleisbau, verwendet (DE 26 38 387).First, the used tires after granulation up to grain sizes of about 25 mm as an additive to the product bituminous road surface layers or sports place fastenings used. To do this, the rubber granules lat in cement mixers common in road construction, Gravel sand or sand, water and adhesion improvers mixed and with the usual road construction machines as hochela tical intermediate layer, for example in the car railway reconstruction or in the construction of road tracks (DE 26 38 387).

Eine zweite Möglichkeit Altreifen als Sekundärrohstoff zu verwerten besteht darin, die Altreifen einer Pyro­ lyse zu unterziehen, um dadurch Pyrolyseöl als Aus­ gangsstoff für chemische Grundstoffe oder Brennöl zur Gewinnung von Wärmeenergie und Elektroenergie durch Ausnutzung der thermischen Energie des Schwelgases durch direkten Antrieb einer Gasturbine zu gewinnen (DE 27 24 813). Dazu werden die Altreifen unterkühlt. Die unterkühlten Reifen werden in der Regel zunächst einem Gummivorbrecher zugeführt, in dem nur der Gummi der Reifen derart vorgebrochen wird, daß er von den Wulst­ drähten gelöst werden kann. Dem Gummivorbrecher wird z. B. eine Doppelrotorhammermühle nachgeschaltet, die die Grundbestandteile von der Karkasse abschlägt, die danach in einer Siebtrommel in verschiedene Korngrößen sortiert werden. Das Gummigranulat wird dann über Mag­ netabscheider und Siebanlagen von den restlichen Metall­ anteilen und Cordfasern getrennt (DE 27 24 813). Anschlie­ ßend werden die Gummibestandteile bei etwa 500°C ent­ gast. Der dabei entstehende Ruß kann entweder als Wei­ terverarbeitungsprodukt oder als Brennstoff verwendet werden. Das durch die Entgasung entstehende Schwelgas wird zum direkten Antrieb einer Gasturbine und somit zur Energieerzeugung genutzt.A second possibility is used tires as a secondary raw material to recycle is the old tires of a pyro undergo lysis to thereby remove pyrolysis oil raw material for chemical raw materials or fuel oil Obtaining heat energy and electrical energy through Utilization of the thermal energy of the carbonization gas to win direct drive of a gas turbine (DE  27 24 813). To do this, the old tires are supercooled. The supercooled tires are usually one Rubber crusher fed in which only the rubber of the Tire is broken in such a way that it comes off the bead wires can be solved. The rubber crusher will e.g. B. downstream of a double rotor hammer mill, the knocks off the basic ingredients from the carcass that then in a sieve drum in different grain sizes be sorted. The rubber granulate is then over Mag net separators and screening plants from the remaining metal share and cord fibers separately (DE 27 24 813). Then The rubber components are removed at around 500 ° C guest. The resulting soot can either be white processing product or used as fuel will. The smoldering gas generated by the degassing becomes the direct drive of a gas turbine and thus the Power generation used.

Eine dritte Möglichkeit, Altreifen als Sekundärrohstoff zu verwenden, besteht darin, feinzerkleinertes Gummi­ granulat, das z. B. bei der Runderneuerung von Altreifen anfallende Gummimehl, vorzugsweise im Extruder zu repla­ stizieren und bis zu 20 Gewichtsanteilen an der Protek­ tormischung bei der Runderneuerung von Altreifen wieder­ zuverwenden. Offensichtliche Nachteile dieses Verfahrens sind die hohen Anlagen- und Energiekosten des Extru­ ders, sowie der Einsatz von Chemikalien, die einen Ketten- und/oder Vernetzerabbau bewirken und die ganz oder teilweise im Replastikat verbleiben. Zudem kann ein nur relativ geringer Anteil der anfallenden Altreifen­ menge durch Regenerierung einer Wiederverwertung zugeführt werden.A third option, used tires as a secondary raw material to use is finely crushed rubber granules, e.g. B. when retreading old tires resulting gum powder, preferably in the extruder to repla and up to 20 parts by weight of the Protek door mix again when retreading old tires to use. Obvious disadvantages of this procedure are the high system and energy costs of the extru ders, as well as the use of chemicals, the one Chain and / or crosslinker degradation and all or remain partially in the replica. In addition, a only a relatively small proportion of used tires quantity by regeneration of a recycling are fed.

Ziel der Erfindung ist es, Altgummi, insbesondere Altrei­ fen, mittels eines biotechnologischen Verfahrens zielge­ richtet soweit aufzuarbeiten, daß eine partielle oder vollständige Wiederverwendung der Inhaltsstoffe des Gum­ mis möglich ist und gleichzeitig Schwefel gewonnen wird. The aim of the invention is to scrap rubber, in particular scrap rubber fen, using a biotechnological process set up to work so far that a partial or complete reuse of the ingredients of the gum mis is possible and sulfur is obtained at the same time.  

Erfindungsgemäß wird diese Aufgabe dadurch gelöst, daß z. B. die Altreifen in geeigneter Art und Weise zerklei­ nert und dann einem Bioreaktor (1) zugeführt werden, in dem sich eine Bakteriensuspension (2) von chemolitho­ trophen Bakterien, vorzugsweise Thiobacillus ferrooxi­ dans oder Thiobacillus thiooxidans, befindet. Bak­ terien der Gattung Thiobacillus sind bei Anwesenheit von Sauerstoff in der Lage, die Sulfidbrücken des Gummis (3) zu spalten und damit das Gummimaterial zu replastizieren, wodurch eine Weiterverarbeitung der vom Schwefel abgespaltenen Kohlenstoffketten und eine Wiederverwendung der von den Bakterien freigesetzten Schwefelverbindungen ermöglicht wird. Dabei werden von den Bakterien in Abhängigkeit vom zugeführten Sauer­ stoff elementarer Schwefel und/oder, Schwefelsäure produziert.According to the invention this object is achieved in that, for. B. Zertlei the old tires in a suitable manner and then fed to a bioreactor ( 1 ) in which there is a bacterial suspension ( 2 ) of chemolitho trophic bacteria, preferably Thiobacillus ferrooxi dans or Thiobacillus thiooxidans. In the presence of oxygen, bacteria of the genus Thiobacillus are able to split the sulfide bridges of the rubber ( 3 ) and thus replastate the rubber material, which enables further processing of the carbon chains separated from the sulfur and reuse of the sulfur compounds released by the bacteria. Elemental sulfur and / or sulfuric acid are produced by the bacteria depending on the oxygen supplied.

Die Zerkleinerung des Altgummis zu Granulat (3) kann dabei nach bekannten Verfahren, wie z. B. durch Abkühlung mit Hilfe von verflüssigtem Stickstoff (DE 28 03 859; DE 21 45 728) oder verfestigtem Kohlendioxid (DE 26 38 387) und anschließender Zerkleinerung in üblichen Mahleinrichtun­ gen, wie z. B. Hammermühlen, bis zu Korngrößen von 1 bis 15 mm, vorzugsweise von 5-7 mm erfolgen. Eine Aufarbei­ tung des bei der Vulkanisation von Altreifen anfallenden Gummimehls ist auch ohne vorherige Zerkleinerung mög­ lich. Das Gummigranulat (3) wird nach der Zer­ kleinerung dem Bioreaktor (1) zugeführt, in dem sich eine Bakteriensuspension (2) bei gleichzeitiger Anwe­ senheit von Sauerstoff befindet. Der Bioreaktor (1) ist so gestaltet, daß entweder ein chargenweiser oder aber ein quasikontinuierlicher bzw. ein kontinuierlicher Aus- und Eintrag des frischen, das heißt des aufzuarbeitenden Gummimaterials und des aufgearbeiteten, schwefelarmen Gummigranulats möglich ist. Diese Aufgabe wird z. B. erfindungsgemäß dadurch gelöst, daß das Gummigranulat in ein oder mehrere Trom­ melkörbe (4), bestehend aus Maschendraht nichtrostenden Stahls, überführt und dem oder den Trommelkörben am oberen Teil des Bioreaktors (1) z. B. mittels einer Hebe­ vorrichtung aufgegeben wird. Der oder die Trommelkörbe (4) sind mit einer Be- bzw. Entladeklappe (5) ausge­ stattet und auf einer Welle (6) derartig gelagert und befestigt, daß ein ständiges und gleichmäßiges Rotie­ ren der Trommelkörbe (4) durch einen mit der Welle (6) gekoppelten Motorantrieb (7) gewährleistet ist. Nach der Aufarbeitung des Gummimaterials werden die Trom­ melkörbe (4) dem Bioreaktor (1) wieder entnommen und das schwefelarme Gummimaterial einer gesonderten Wei­ terverarbeitung zugeführt. Durch die ständige Rotation der mit Gummigranulat (3) gefüllten Trommelkörbe (4), welche zu etwa 30-40 Mengenanteilen, vorzugsweise 30- 35 Mengenanteilen des eingefüllten Gummigranulats (4) in die Bakteriensuspension eintauchen, wird das Gum­ migranulat (4) kontinuierlich von der sich im Bioreaktor (1) befindenden Bakteriensuspension (2) umspült.The crushing of the waste rubber to granules ( 3 ) can be done by known methods, such as. B. by cooling with the help of liquefied nitrogen (DE 28 03 859; DE 21 45 728) or solidified carbon dioxide (DE 26 38 387) and subsequent comminution in conventional milling devices, such as. B. hammer mills, up to grain sizes of 1 to 15 mm, preferably from 5-7 mm. A processing of the rubber powder resulting from the vulcanization of old tires is also possible without prior crushing. The rubber granulate ( 3 ) is fed to the bioreactor ( 1 ) after the crushing, in which there is a bacterial suspension ( 2 ) with simultaneous presence of oxygen. The bioreactor ( 1 ) is designed so that either batchwise or quasi-continuous or continuous discharge and entry of the fresh, that is to say the rubber material to be refurbished and the refurbished, low-sulfur rubber granulate is possible. This task is done e.g. B. solved according to the invention in that the rubber granules in one or more drum trays ( 4 ), consisting of wire mesh stainless steel, transferred and the drum trays or baskets on the upper part of the bioreactor ( 1 ) z. B. is abandoned by means of a lifting device. The one or more drum baskets ( 4 ) are equipped with a loading or unloading flap ( 5 ) and are mounted and fastened on a shaft ( 6 ) in such a way that a constant and uniform rotation of the drum baskets ( 4 ) by a with the shaft ( 6 ) coupled motor drive ( 7 ) is guaranteed. After working up the rubber material, the drum baskets ( 4 ) are removed from the bioreactor ( 1 ) and the low-sulfur rubber material is fed to a separate processing unit. Due to the constant rotation of the drum baskets ( 4 ) filled with rubber granules ( 3 ), which about 30-40 parts, preferably 30-35 parts, of the filled rubber granules ( 4 ) are immersed in the bacterial suspension, the gum migrates ( 4 ) continuously from the bacteria suspension ( 2 ) located in the bioreactor ( 1 ).

Der Bioreaktor (1) kann z. B. als Becken gestaltet sein, an dessen Flüssigkeitsoberfläche die Trommelkörbe (4) ro­ tieren, so daß ein ausreichender Kontakt zwischen der Bakteriensuspension (2) und dem Gummigranulat (3) gewähr­ leistet wird. Weiterhin wird durch das Rotieren der Trom­ melkörbe (4) an der Flüssigkeitsoberfläche eine Vergröße­ rung der Stoffübergangsfläche zwischen Flüssigkeit und Luft erreicht, so daß auf eine gesonderte Sauerstoffver­ sorgung zur Begasung der Flüssigkeit verzichtet den kann.The bioreactor ( 1 ) can e.g. B. be designed as a pool, on the liquid surface of the drum baskets ( 4 ) ro animals, so that sufficient contact between the bacterial suspension ( 2 ) and the rubber granulate ( 3 ) is guaranteed. Furthermore, by rotating the drum trays ( 4 ) on the liquid surface, an enlargement of the mass transfer surface between liquid and air is achieved, so that a separate oxygen supply for fumigation of the liquid can be dispensed with.

Der Bakteriensuspension (2) wird ständig oder in be­ stimmten Zeitintervallen, beispielsweise täglich, eine definierte Menge an Nährlösung und Spurenelementen (8) zugegeben. Der pH-Wert der Bakteriensuspension (2) wird ständig mit einer kontinuierlichen pH-Meßeinrichtung (9) gemessen und auf die für die Aufarbeitung optimalen pH- Werte zwischen 1 und 4, vorzugsweise zwischen pH 1,5 und pH 2,5 eingestellt. Die Regelung des pH-Wertes auf pH- Werte zwischen 1 und 2,5 kann durch Zugabe der notwendi­ gen Nährlösung (8) und/oder durch Zugabe von Chemikalien (10) über eine Zuteileinrichtung (11) realisiert werden. Als weitere Ausführungsform des Bioreaktors sind z. B. Haldenreaktoren, ähnlich denen wie sie bei Laugungspro­ zessen von Armerzen angewendet werden, beschrieben z. B. in Torma, A.E. "Current standing heap, dump, in-situ leaching technology of copper"; Metall 38 (1984) S. 1044-1047, möglich.The bacterial suspension ( 2 ) is added continuously or at certain time intervals, for example daily, a defined amount of nutrient solution and trace elements ( 8 ). The pH value of the bacterial suspension ( 2 ) is continuously measured with a continuous pH measuring device ( 9 ) and adjusted to the optimal pH values between 1 and 4, preferably between pH 1.5 and pH 2.5, for the work-up. The regulation of the pH value to pH values between 1 and 2.5 can be realized by adding the necessary nutrient solution ( 8 ) and / or by adding chemicals ( 10 ) via an allocation device ( 11 ). As a further embodiment of the bioreactor, for. B. stockpile reactors, similar to those used in processes of laryngeal pain described for. B. in Torma, AE "Current standing heap, dump, in-situ leaching technology of copper"; Metall 38 (1984) pp. 1044-1047, possible.

Bei einem für die Bakterien limitierten Sauerstoffein­ trag erfolgt vorrangig eine Oxidation des im Gummi­ gebundenen Schwefels zu elementarem Schwefel. Ein Teil der Bakteriensuspension (2) wird mit dem von den Bak­ terien produzierten Schwefel am Boden des Bioreaktors (1) über eine Pumpe (12) abgezogen und einer Separa­ tionsstufe (13), beispielsweise einem Hydrozyklon, zur Abtrennung des Schwefels zugeführt. Nach Abtren­ nung des Schwefels in der Separationsstufe wird die vom Schwefel befreite Suspension (14) dem Bioreaktor (1) erneut zugeführt.If the oxygen input is limited for the bacteria, the sulfur bound in the rubber is primarily oxidized to elemental sulfur. Part of the bacterial suspension ( 2 ) is withdrawn with the sulfur produced by the bacteria at the bottom of the bioreactor ( 1 ) via a pump ( 12 ) and fed to a separation stage ( 13 ), for example a hydrocyclone, to separate the sulfur. After the sulfur has been removed in the separation stage, the suspension ( 14 ) which has been freed from sulfur is fed to the bioreactor ( 1 ) again.

Bei unlimitiertem Sauerstoffeintrag erfolgt vorrangig eine Oxidation des im Gummi gebundenen Schwefels zu Schwefelsäure. Diese wird aus dem Bioreaktor abgezogen und aufkonzentriert bzw. neutralisiert. In the case of unlimited oxygen entry, priority is given oxidation of the sulfur bound in the rubber Sulfuric acid. This is withdrawn from the bioreactor and concentrated or neutralized.  

Verzeichnis der verwendeten FormelzeichenList of the formula symbols used

 1 - Bioreaktor
 2 - Bakteriensuspension
 3 - Gummimaterial
 4 - Trommelkörbe
 5 - Be- und Entladeklappe
 6 - Welle
 7 - Motorantrieb
 8 - Nährlösung und Spurenelemente
 9 - kontinuierliche pH-Meßeinrichtung
10 - Chemikalien
11 - Zuteileinrichtung
12 - Pumpe
13 - Separationsstufe
14 - Schwefelarme Bakteriensuspension
15 - Schwefel 1 - bioreactor
2 - bacterial suspension
3 - rubber material
4 - drum baskets
5 - Loading and unloading hatch
6 - wave
7 - Motor drive
8 - Nutrient solution and trace elements
9 - continuous pH measuring device
10 - chemicals
11 - Allotment facility
12 - pump
13 - separation stage
14 - Low sulfur bacterial suspension
15 - sulfur

Claims (6)

1. Verfahren zur biologischen Aufarbeitung von Altgummi mit dem Ziel der Wiederverwendung desselben gekennzeich­ net dadurch, daß Gummiabfälle biologisch aufgearbeitet werden und elementarer Schwefel wiedergewonnen wird, derart, daß Gummiabfälle in einem Bioreaktor, in dem sich eine Bakteriensuspension von chemolithotrophen Mikroorganismen unter definierter Sauerstoffzufuhr be­ findet, zugeführt werden und der Altgummi vom Schwefel teilweise bzw. vollständig biologisch befreit wird.1. Process for the biological processing of waste rubber with the aim of reusing the same, characterized in that rubber waste is biologically processed and elemental sulfur is recovered in such a way that rubber waste in a bioreactor in which a bacterial suspension of chemilithotrophic microorganisms with a defined supply of oxygen is found , are supplied and the waste rubber is partially or completely biologically removed from the sulfur. 2. Verfahren nach Anspruch 1 gekennzeichnet dadurch, daß der pH-Wert der Bakteriensuspension mittels konti­ nuierlicher pH-Meßeinrichtung gemessen und durch geregelte Zugabe von Nährlösung und/oder einer Chemi­ kalie, beispielsweise NaOH, auf pH-Werte zwischen 1 und 4, vorzugsweise auf pH-Werte zwischen 1,5 und 2,5 eingestellt wird.2. The method according to claim 1, characterized in that the pH value of the bacterial suspension using continuous Nuier pH measuring device measured and by controlled addition of nutrient solution and / or a chemical potash, for example NaOH, to pH values between 1 and 4, preferably to pH values between 1.5 and 2.5 is set. 3. Verfahren nach Anspruch 1 und 2 gekennzeichnet dadurch, daß der pH-Wert der Bakteriensuspension durch geregelte Sauerstoffzufuhr einstellbar ist.3. The method according to claim 1 and 2, characterized in that that the pH of the bacterial suspension is regulated by Oxygenation is adjustable. 4. Verfahren nach Anspruch 3 gekennzeichnet dadurch, daß je nach Sauerstoffzufuhr der im Gummi enthaltene Schwefel zu elementarem Schwefel oder zu sauerstoffhaltigen Schwefelverbindungen oxidiert wird.4. The method according to claim 3, characterized in that each after the oxygen supply, the sulfur contained in the rubber to elemental sulfur or to oxygenated ones Sulfur compounds is oxidized. 5. Verfahren nach Anspruch 2 gekennzeichnet dadurch, daß die durch die Oxidation produzierten sauerstoffhal­ tigen Verbindungen aufkonzentriert und oder neutrali­ siert werden.5. The method according to claim 2, characterized in that the oxygen halides produced by the oxidation concentrated compounds and or neutral be settled. 6. Vorrichtung zur Realisierung des Verfahrens nach An­ spruch 1 gekennzeichnet dadurch, daß der Bioreaktor, in dem sich die Bakteriensuspension befindet, als biologisches Becken, auf dessen Flüssigkeitsober­ fläche sich rotierende Siebtrommeln befinden, oder als Haldenreaktor gestaltet ist.6. Device for implementing the method according to An saying 1 characterized in that the bioreactor,  in which the bacterial suspension is located, as biological tank, on the upper surface of the liquid rotating screen drums, or as Heap reactor is designed.
DE19904042009 1990-12-22 1990-12-22 Process for the biological processing of waste rubber Expired - Fee Related DE4042009C2 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
DE19904042009 DE4042009C2 (en) 1990-12-22 1990-12-22 Process for the biological processing of waste rubber
DK91121471T DK0493732T3 (en) 1990-12-22 1991-12-14 Process and device for reprocessing of old rubber
AT91121471T ATE136942T1 (en) 1990-12-22 1991-12-14 METHOD FOR REPROCESSING USED RUBBER
ES91121471T ES2086468T3 (en) 1990-12-22 1991-12-14 PROCEDURE FOR THE TREATMENT OF OLD RUBBER RECOVERY.
EP19910121471 EP0493732B1 (en) 1990-12-22 1991-12-14 Process for processing of old rubber
DE59107689T DE59107689D1 (en) 1990-12-22 1991-12-14 Process for processing used rubber
CA 2058160 CA2058160C (en) 1990-12-22 1991-12-20 Method for processing scrap rubber
US07/811,629 US5275948A (en) 1990-12-22 1991-12-23 Method for reprocessing scrap rubber
JP34059291A JP2546942B2 (en) 1990-12-22 1991-12-24 Old rubber processing method
GR960401305T GR3019940T3 (en) 1990-12-22 1996-05-16 Process for processing of old rubber

Applications Claiming Priority (1)

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DE19904042009 DE4042009C2 (en) 1990-12-22 1990-12-22 Process for the biological processing of waste rubber

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DE4042009A1 true DE4042009A1 (en) 1992-06-25
DE4042009C2 DE4042009C2 (en) 1999-09-09

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DE59107689T Expired - Lifetime DE59107689D1 (en) 1990-12-22 1991-12-14 Process for processing used rubber

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EP (1) EP0493732B1 (en)
JP (1) JP2546942B2 (en)
AT (1) ATE136942T1 (en)
CA (1) CA2058160C (en)
DE (2) DE4042009C2 (en)
DK (1) DK0493732T3 (en)
ES (1) ES2086468T3 (en)
GR (1) GR3019940T3 (en)

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US7425584B2 (en) * 2004-11-29 2008-09-16 Alberta Research Council Catalytic devulcanization of rubber
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JP2011199494A (en) 2010-03-18 2011-10-06 Panasonic Corp Antenna unit, and electronic apparatus including the same
FR2965270B1 (en) * 2010-09-24 2014-11-07 Eiffage Travaux Publics BITUMEN AND RUBBER BINDER FOR PAVEMENT COATING OR THE LIKE, PROCESS FOR PRODUCING THE SAME AND USES THEREOF
CN103923945B (en) * 2014-04-16 2016-08-24 北京化工大学 A kind of method utilizing microbial bacteria desulfurization regeneration scrap rubber
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JPH04305282A (en) 1992-10-28
EP0493732A1 (en) 1992-07-08
JP2546942B2 (en) 1996-10-23
US5275948A (en) 1994-01-04
ATE136942T1 (en) 1996-05-15
ES2086468T3 (en) 1996-07-01
DE4042009C2 (en) 1999-09-09
GR3019940T3 (en) 1996-08-31
CA2058160A1 (en) 1992-06-23
DE59107689D1 (en) 1996-05-23
EP0493732B1 (en) 1996-04-17
DK0493732T3 (en) 1996-05-13
CA2058160C (en) 2002-06-25

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